Thermosetting polyurethane material for a golf ball cover

ABSTRACT

A curative blend for a thermosetting polyurethane material that allows for a polyurethane material with greater durability is disclosed herein. The curative blend is composed of 4,4″-methylenebis-(2,6-diethyl)-aniline and a second curing agent. A preferred polyurethane prepolymer is polytetramethylene ether glycol terminated toluene diisocyanate prepolymer. The thermosetting polyurethane is preferably utilized as a cover for a golf ball. The cover is preferably formed over a core and boundary layer.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] Not Applicable

FEDERAL RESEARCH STATEMENT

[0002] [Not Applicable]

BACKGROUND OF INVENTION

[0003] 1. Field of the Invention

[0004] The present invention relates to a thermosetting polyurethanematerial. More specifically, the present invention relates to athermosetting polyurethane material for a cover of a golf ball.

[0005] 2. Description of the Related Art

[0006] Conventionally golf balls are made by molding a cover around acore. The core may be wound or solid. A wound core typically compriseselastic thread wound about a solid or liquid center. Unlike wound cores,solid cores do not include a wound elastic thread layer. Solid corestypically may comprise a single solid piece center or a solid centercovered by one or more mantle or boundary layers of material.

[0007] The cover may be injection molded, compression molded, or castover the core. Injection molding typically requires a mold having atleast one pair of mold cavities, e.g., a first mold cavity and a secondmold cavity, which mate to form a spherical recess. In addition, a moldmay include more than one mold cavity pair.

[0008] In one exemplary injection molding process each mold cavity mayalso include retractable positioning pins to hold the core in thespherical center of the mold cavity pair. Once the core is positioned inthe first mold cavity, the respective second mold cavity is mated to thefirst to close the mold. A cover material is then injected into theclosed mold. The positioning pins are retracted while the cover materialis flowable to allow the material to fill in any holes caused by thepins. When the material is at least partially cured, the covered core isremoved from the mold.

[0009] As with injection molding, compression molds typically includemultiple pairs of mold cavities, each pair comprising first and secondmold cavities that mate to form a spherical recess. In one exemplarycompression molding process, a cover material is pre-formed intohalf-shells, which are placed into a respective pair of compression moldcavities. The core is placed between the cover material half-shells andthe mold is closed. The core and cover combination is then exposed toheat and pressure, which cause the cover half-shells to combine and forma full cover.

[0010] As with the above-referenced processes, a casting process alsoutilizes pairs of mold cavities. In a casting process, a cover materialis introduced into a first mold cavity of each pair. Then, a core isheld in position (e.g. by an overhanging vacuum or suction apparatus) tocontact the cover material in what will be the spherical center of themold cavity pair. Once the cover material is at least partially cured(e.g., a point where the core will not substantially move), the core isreleased, the cover material is introduced into a second mold cavity ofeach pair, and the mold is closed. The closed mold is then subjected toheat and pressure to cure the cover material thereby forming a cover onthe core. With injection molding, compression molding, and casting, themolding cavities typically include a negative dimple pattern to impart adimple pattern on the cover during the molding process.

[0011] Materials previously used as golf ball covers include balata(natural or synthetic), gutta-percha, ionomeric resins (e.g., DuPont'sSURLYN®), and polyurethanes. Balata is the benchmark cover material withrespect to sound (i.e. the sound made when the ball is hit by a golfclub) and feel (i.e. the sensation imparted to the golfer when hittingthe ball). Natural balata is derived from the Bully Gum tree, whilesynthetic balata is derived from a petroleum compound. Balata isexpensive compared to other cover materials, and golf balls covered withbalata tend to have poor durability (i.e. poor cut and shearresistance). Gutta percha is derived from the Malaysian sapodilla tree.A golf ball covered with gutta percha is considered to have a harshsound and feel as compared to balata covered golf balls.

[0012] Ionomeric resins, as compared to balata, are typically lessexpensive and tend to have good durability. However, golf balls havingionomeric resin covers typically have inferior sound and feel,especially as compared to balata covers.

[0013] A golf ball with a polyurethane cover generally has greaterdurability than a golf ball with a balata cover. The polyurethanecovered golf ball generally has a better sound and feel than a golf ballwith an ionomeric resin cover. Polyurethanes may be thermoset orthermoplastic. Polyurethanes are formed by reacting a prepolymer with apolyfunctional curing agent, such as a polyamine or a polyol. Thepolyurethane prepolymer is the reaction product of, for example, adiisocyanate and a polyol such as a polyether or a polyester. Severalpatents describe the use of polyurethanes in golf balls. However, golfballs with polyurethane covers usually do not have the distance of othergolf balls such as those with covers composed of SURLYN® materials.

[0014] Gallagher, U.S. Pat. No. 3,034,791 discloses a polyurethane golfball cover prepared from the reaction product of poly(tetramethyleneether) glycol and toluene-2,4-diisocyanates (TDI), either pure TDI or anisomeric mixture.

[0015] Isaac, U.S. Pat. No. 3,989,568 (the '568 patent) discloses apolyurethane golf ball cover prepared from prepolymers and curing agentsthat have different rates of reaction so a partial cure can be made. The'568 patent explains that the minimum number of reactants is three.Specifically, in '568 patent, two or more polyurethane prepolymers arereacted with at least one curing agent, or at least one polyurethaneprepolymer is reacted with two or more curing agents as long as thecuring agents have different rates of reaction. The '568 patent alsoexplains that [o]ne of the great advantages of polyurethane covers madein accordance with the instant invention is that they may be made verythin . . . , and [t]here is no limitation on how thick the cover of thepresent invention may be but it is generally preferred . . . that thecover is no more than about 0.6 inches in thickness. The examples in the'568 patent only disclose golf balls having covers that are about 0.025inches thick.

[0016] Similar to Isaac, PCT International Publication Number WO99/43394 to Dunlop Maxfli Sports Corporation, discloses using two curingagents to control the reaction time for polyurethane formation. The twocuring agents are a dimethylthio 2,4-toluenediamine and diethyl2,4-toluenediamine, which are blended to control the reaction rate of atoluene diisocyanate based polyurethane prepolymer or a4,4′-diphenylmethane diisocyanate based polyurethane prepolymer.

[0017] Dusbiber, U.S. Pat. No. 4,123,061 (the '061 patent)discloses apolyurethane golf ball cover prepared from the reaction product of apolyether, a diisocyanate and a curing agent. The '061 patent disclosesthat the polyether may be polyalkylene ether glycol orpolytetramethylene ether glycol. The '061 patent also discloses that thediisocyanate may be TDI, 4,4′-diphenylmethane diisocyanate (MDI), and3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI). Additionally, the'061 patent discloses that the curing agent may be either a polyol(either tri- or tetra-functional and not di-functional) such astriisopropanol amine (TIPA) or trimethoylol propane (TMP), or anamine-type having at least two reactive amine groups such as: 3,3′dichlorobenzidene; 3,3′ dichloro 4,4′ diamino diphenyl methane (MOCA);N,N,N′,N′ tetrakis (2-hydroxy propyl) ethylene diamine; or Uniroyal'sCuralon L which is an aromatic diamine mixture.

[0018] Hewitt, et al., U.S. Pat. No. 4,248,432 (the '432 patent)discloses a thermoplastic polyesterurethane golf ball cover formed froma reaction product of a polyester glycol (molecular weight of 800-1500)(aliphatic diol and an aliphatic dicarboxylic acid) with apara-phenylene diisocyanate (PPDI) or cyclohexane diisocyanate in thesubstantial absence of curing or crosslinking agents. The '432 patentteaches against the use of chain extenders in making polyurethanes. The'432 patent states, when small amounts of butanediol-1,4 are mixed witha polyester . . . the addition results in polyurethanes that do not havethe desired balance of properties to provide good golf ball covers.Similarly, the use of curing or crosslinking agents is not desired . . ..

[0019] Holloway, U.S. Pat. No. 4,349,657 (the '657 patent) discloses amethod for preparing polyester urethanes with PPDI by reacting apolyester (e.g. prepared from aliphatic glycols having 2-8 carbonsreacted with aliphatic dicarboxylic acids having 4-10 carbons) with amolar excess of PPDI to obtain an isocyanate-terminated polyesterurethane (in liquid form and stable at reaction temperatures), and thenreacting the polyester urethane with additional polyester. The '657patent claims that the benefit of this new process is the fact that acontinuous commercial process is possible without stability problems.The '657 patent further describes a suitable use for the resultantmaterial to be golf ball covers.

[0020] Wu, U.S. Pat. No. 5,334,673 (the '673 patent) discloses apolyurethane prepolymer cured with a slow-reacting curing agent selectedfrom slow-reacting polyamine curing agents and difunctional glycols(i.e., 3,5-dimethylthio-2,4-toluenediamine,3,5-dimethylthio-2,6-toluenediamine, N,N′-dialkyldiamino diphenylmethane, trimethyleneglycol-di-p-aminobenzoate,polytetramethyleneoxide-di-p-aminobenzoate, 1,4-butanediol,2,3-butanediol, 2,3-dimethyl-2,3-butanediol, ethylene glycol, andmixtures of the same). The polyurethane prepolymer in the '673 patent isdisclosed as made from a polyol (e.g., polyether, polyester, orpolylactone) and a diisocyanate such as MDI or TODI. The polyetherpolyols disclosed in the '673 patent are polytetramethylene etherglycol, poly(oxypropylene) glycol, and polybutadiene glycol. Thepolyester polyols disclosed in the '673 patent are polyethylene adipateglycol, polyethylene propylene adipate glycol, and polybutylene adipateglycol. The polylactone polyols disclosed in the '673 patent arediethylene glycol initiated caprolactone, 1,4-butanediol initiatedcaprolactone, trimethylol propane initiated caprolactone, and neopentylglycol initiated caprolactone.

[0021] Cavallaro, et al., U.S. Pat. No. 5,688,191 discloses a golf ballhaving core, mantle layer and cover, wherein the mantle layer is eithera vulcanized thermoplastic elastomer, functionalized styrene-butadieneelastomer, thermoplastic polyurethane, metallocene polymer or blends ofthe same and thermoset materials.

[0022] Wu, et al., U.S. Pat. No. 5,692,974 discloses golf balls havingcovers and cores that incorporate urethane ionomers (i.e. using analkylating agent to introduce ionic interactions in the polyurethane andthereby produce cationic type ionomers).

[0023] Sullivan, et al., U.S. Pat. No. 5,803,831 (the '831 patent)discloses a golf ball having a multi-layer cover wherein the inner coverlayer has a hardness of at least 65 Shore D and the outer cover layerhas a hardness of 55 Shore D or less, and more preferably 48 Shore D orless. The '831 patent explains that this dual layer constructionprovides a golf ball having soft feel and high spin on short shots, andgood distance and average spin on long shots. The '831 patent providesthat the inner cover layer can be made from high or low acid ionomerssuch as SURLYN®, ESCOR® or IOTEK®, or blends of the same, nonionomericthermoplastic material such as metallocene catalyzed polyolefins orpolyamides, polyamide/ionomer blends, polyphenylene ether/ionomerblends, etc., (having a Shore D hardness of at least 60 and a flexmodulus of more than 30000 psi), thermoplastic or thermosettingpolyurethanes, polyester elastomers (e.g. HYTREL®), or polyether blockamides (e.g. PEBAX®), or blends of these materials. The '831 patent alsoprovides that the outer cover layer can be made from soft low modulus(i.e. 1000-10000 psi) material such as low-acid ionomers, ionomericblends, non-ionomeric thermoplastic or thermosetting materials such aspolyolefins, polyurethane (e.g. thermoplastic polyurethanes like TEXIN®,PELETHANE®, and thermoset polyurethanes like those disclosed in Wu, U.S.Pat. No. 5,334,673), polyester elastomer (e.g. HYTREL®), or polyetherblock amide (e.g. PEBAX®), or a blend of these materials.

[0024] Hebert, et al., U.S. Pat. No. 5,885,172 (the '172 patent)discloses a multilayer golf ball giving a progressive performance (i.e.different performance characteristics when struck with different clubsat different head speeds and loft angles) and having an outer coverlayer formed of a thermoset material with a thickness of less than 0.05inches and an inner cover layer formed of a high flexural modulusmaterial. The '172 patent provides that the outer cover is made frompolyurethane ionomers as described in Wu, et al., U.S. Pat. No.5,692,974, or thermoset polyurethanes such as TDI ormethylenebis-(4-cyclohexyl isocyanate) (HMDI), or a polyol cured with apolyamine (e.g. methylenedianiline (MDA)), or with a trifunctionalglycol (e.g., N,N,N′,N″-tetrakis(2-hydroxpropyl)ethylened iamine). The'172 also provides that the inner cover has a Shore D hardness of 65-80,a flexural modulus of at least about 65,000 psi, and a thickness ofabout 0.020-0.045 inches. Exemplary materials for the inner cover areionomers, polyurethanes, polyetheresters (e.g. HYTREL®), polyetheramides(e.g., PEBAX®), polyesters, dynamically vulcanized elastomers,functionalized styrene-butadiene elastomer, metallocene polymer, blendsof these materials, nylon or acrylonitrile-butadiene-styrene copolymer.

[0025] Wu, U.S. Pat. No. 5,484,870 (the '870 patent) discloses golfballs having covers composed of a polyurea composition. The polyureacomposition disclosed in the '870 patent is a reaction product of anorganic isocyanate having at least two functional groups and an organicamine having at least two functional groups. One of the organicisocyanates disclosed by the '870 patent is PPDI.

[0026] Although the prior art has disclosed golf ball covers composed ofmany different polyurethane materials, none of these golf balls haveproven completely satisfactory. Dissatisfaction, for example, remainswith processing and manufacturing the balls, especially with controllingthe reaction time of the curative and prepolymer. If the gel time forformation of a polyurethane material is too fast, the time to place acore in a hemispherical cavity with the gelling pre-polyurethanematerial and to mate the hemispherical cavity with a correspondinghemispherical cavity is greatly reduced thereby leading to processingproblems like air pockets, and centering of the core.

SUMMARY OF INVENTION

[0027] The present invention is a more durable polyurethane material fora golf ball cover. The polyurethane material is formed from at least onepolyurethane prepolymer and a curing agent comprising4,4′-methylenebis-(2,6-diethyl)-aniline.

[0028] Another aspect of the present invention is a polyurethanematerial formed from at least one polyurethane prepolymer and curativeblend composed of 4,4′-methylenebis-(2,6-diethyl)-aniline and a secondcuring agent having the same equivalent weight as4,4′-methylenebis-(2,6-diethyl)-aniline. The equivalent weight of acompound is determined by dividing its molecular weight by the number ofits functionality groups.

BRIEF DESCRIPTION OF DRAWINGS

[0029]FIG. 1 illustrates a perspective view of a golf ball of thepresent invention including a cut-away portion showing a core, aboundary layer, and a cover.

[0030]FIG. 2 illustrates a perspective view of a golf ball of thepresent invention including a cut-away portion core and a cover.

DETAILED DESCRIPTION

[0031] As illustrated in FIG. 1, a golf ball is generally indicated as10. The golf ball 10 preferably includes a core 12, a boundary layer 14and a cover 16. Alternatively, as shown in FIG. 2, the golf ball 10 mayonly include a core 12 and a cover 16. The cover 16 is composed of athermosetting polyurethane material of the present invention. In apreferred embodiment, the cover 16 is formed over a boundary layer 14and core 12, as shown in FIG. 1. Alternatively, the cover 16 is formedover the core 12, as shown in FIG. 2. Those skilled in the art willrecognize that the core may be solid, hollow, multi-piece orliquid-filled, the boundary layer may be partitioned into additionallayers, and the golf ball may have a wound layer without departing fromthe scope and spirit of the present invention.

[0032] The polyurethane material of the present invention is formed fromreactants comprising at least one polyurethane prepolymer and a curativecomprising a 4,4′-methylenebis-(2,6-diethyl)-aniline. The4,4′-methylenebis-(2,6-diethyl)-aniline is preferably present in anamount of 25 to 75 parts per one hundred parts of the curative blend,more preferably 30 to 70 parts per one hundred parts of the curativeblend, even more preferably 35 to 65 parts per one hundred parts of thecurative blend, and most preferably 50 parts per one hundred parts ofthe curative blend. The 4,4′-methylenebis-(2,6-diethyl)-aniline has anequivalent weight of 155, and a molecular weight of 310. A preferred4,4′-methylenebis-(2,6-diethyl)-aniline is available from LONZAGROUPunder the brand name LONZACURE M-DEA.

[0033] A preferred second curative component of a curative blend used ina polyurethane material of the present invention is preferablyN,N′-dialkylamino-diphenyl-methane. TheN,N′-dialkylamino-diphenyl-methane is preferably present in an amount of25 to 100 parts per one hundred parts of the curative blend, morepreferably 25 to 75 parts per one hundred parts of the curative blend,yet more preferably 30 to 70 parts per one hundred parts of the curativeblend, even more preferably 35 to 65 parts per one hundred parts of thecurative blend, and most preferably 50 parts per one hundred parts ofthe curative blend. A preferred N,N′-dialkylamino-diphenyl-methane isavailable from UOP Company under the brand name UNILINK 4200.

[0034] The N,N′-dialkylamino-diphenyl-methane is an aromatic secondarydiamine chain extender for polyurethane polymers, and it has a slowerrate of reaction than conventional aromatic amines. When used in acurative blend, the N,N′-dialkylamino-diphenyl-methane slows thereaction and lowers the temperature of the reaction. TheN,N′-dialkylamino-diphenyl-methane has an equivalent weight of 155, anda molecular weight of 310. The secondary diamine of theN,N′-dialkylamino-diphenyl-methane has a labile hydrogen and an alkylgroup.

[0035] An alternative second curative component of a curative blend usedin a polyurethane material of the present invention is adimethylthio-2,4-toluene-diamine, which is available from AlbemarleCorporation of Baton Rouge, La. under the tradename ETHACURE®300.

[0036] The polyurethane prepolymer is preferably selected from toluenediisocyanate-based polyurethane prepolymers, para-phenylenediisocyanate-based polyurethane prepolymers, and 4,4′-diphenylmethanediisocyanate-based polyurethane prepolymers. The polyurethane prepolymeris preferably utilized alone or in a blend of two or three polyurethaneprepolymers.

[0037] The polyurethane prepolymer is most preferably a toluenediisocyanate-based polyurethane prepolymer such as a polypropyleneglycol terminated toluene diisocyanate prepolymer or apolytetramethylene ether glycol terminated toluene diisocyanateprepolymer. A preferred polypropylene glycol terminated toluenediisocyanate prepolymer is available from Uniroyal Chemical Company ofMiddlebury, Conn., under the tradename ADIPRENE® LFG960. A preferredpolytetramethylene ether glycol terminated toluene diisocyanateprepolymer (NCO content 5%) is available from Uniroyal Chemical Companyof Middlebury, Conn., under the tradename ADIPRENE® LF930. Anothertoluene diisocyanate prepolymer is a polytetramethylene ether glycolterminated toluene diisocyanate prepolymer (NCO content 6%) availablefrom Uniroyal Chemical Company of Middlebury, Conn., under the tradenameADIPRENE® LF950. The use of multiple polyurethane prepolymers is setforth in U.S. Pat. No. 6,190,268, entitled Golf Ball With A PolyurethaneCover, filed on Jul. 27, 1999, assigned to Callaway Golf Company, andwhich is hereby incorporated by reference in its entirety.

[0038] An alternative polyurethane prepolymer is a para-phenylenediisocyanate-based polyurethane prepolymer such as para-phenylenediisocyanate terminated polyester prepolymer, which is available fromUniroyal Chemical under the tradename ADIPRENE® LFPX 2950, orpara-phenylene diisocyanate terminated polyether prepolymer, which isavailable from Uniroyal Chemical under the tradename ADIPRENE® LFPX 950.

[0039] The ratio of the polyurethane prepolymer to curative isdetermined by the nitrogen-carbon-oxygen group (NCO) content of thepolyurethane prepolymer. For example, the NCO content of thepolypropylene glycol terminated toluene diisocyanate prepolymer ispreferably in the range of 3.0% to 6.0%, more preferably in the range of4.0% to 5.75%, and most preferably 5.70%. The NCO content of thepolytetramethylene ether glycol terminated toluene diisocyanateprepolymer is preferably in the range of 3.75% to 7.0%, more preferablyin the range of 4.0% to 6.5%, and most preferably 5% or 6%. The weightratio of the polyurethane prepolymer to the curative is preferably inthe range of about 10:1 to about 30:1.

[0040] Prior to curing, the polyurethane prepolymer and curative blendare preferably stored separately. In general, the polyurethane materialis formed by first heating and mixing the curative blend. Then, thepolyurethane prepolymer and the curative blend are mixed in a chamber.The mixture from the chamber is dispensed into a hemispherical cavityprior to insertion of a golf ball precursor product. Thepre-polyurethane material is cured by applying heat and pressure for apredetermined time period. A more specific process is set forth below.

[0041] The polyurethane prepolymer is preferably degassed and warmed ina first holding container. The processing temperature for thepolyurethane prepolymer is preferably in the range of about 70-130° F.,and most preferably in the range of about 80-120° F. The polyurethaneprepolymer is preferably flowable from the first holding container to amixing chamber in a range of about 200-1100 grams of material perminute, or as needed for processing. In addition, the polyurethaneprepolymer may be agitated in the first holding container, in the rangeof 0-250 rpm, to maintain a more even distribution of material and toeliminate crystallization.

[0042] The curative blend is degassed and warmed in a second holdingcontainer. The processing temperature for the curative blend ispreferably in the range of about 50-230° F., and more preferably in therange of about 80-210° F., and most preferably in the range of about170-190° F. The curative is preferably flowable from the second holdingcontainer to the mixing chamber in the range of about 15-75 grams ofmaterial per minute, or as needed. Additives may be added to thecurative blend as desired.

[0043] The polyurethane prepolymer and curative blend are preferablyadded to the common mixing chamber at a temperature in the range ofabout 160-220° F. A colorant material, such as, for example, titaniumdioxide, barium sulfate, and/or zinc oxide in a glycol or castor oilcarrier, and/or other additive material(s) as are well known in the art,may be added to the common mixing chamber. The amount of colorantmaterial added is preferably in the range of about 0-10% by weight ofthe combined polyurethane prepolymer and curative materials, and morepreferably in the range of about 2-8%. Other additives, such as, forexample, polymer fillers, metallic fillers, and/or organic and inorganicfillers (e.g. polymers, balata, ionomers, etc.) may be added as well toincrease the specific gravity of the polyurethane material. The entiremixture is preferably agitated in the mixing chamber in the range ofabout 1 to 250 rpm prior to molding. A more detailed explanation of oneaspect of the process is set forth in U.S. Pat. No. 6,200,512, entitledGolf Balls And Methods Of Manufacturing The Same, filed on Apr. 20,1999, assigned to Callaway Golf Company, and which is herebyincorporated by reference in its entirety. A more detailed explanationof the casting system is set forth in U.S. Pat. No. 6,395,218, entitledMethod For Forming A Thermoset Golf Ball Cover, filed on Feb. 1, 2000,assigned to Callaway Golf Company, and which is hereby incorporated byreference in its entirety.

[0044] The core 12 of the golf ball 10 is generally composed of a blendof a base rubber, a cross-linking agent, a free radical initiator, andone or more fillers or processing aids. A preferred base rubber is apolybutadiene having a cis-1,4 content above 90%, and more preferably98% or above.

[0045] The use of cross-linking agents in a golf ball core is wellknown, and metal acrylate salts are examples of such cross-linkingagents. For example, metal salt diacrylates, dimethacrylates, ormono(meth)acrylates are preferred for use in the golf ball cores of thepresent invention, and zinc diacrylate is a particularly preferredcross-linking agent. A commercially available suitable zinc diacrylateis SR-416 available from Sartomer Co., Inc., Exton, Pa. Other metal saltdi- or mono-(meth)acrylates suitable for use in the present inventioninclude those in which the metal is calcium or magnesium. In themanufacturing process it may be beneficial to pre-mix some cross-linkingagent(s), such as, e.g., zinc diacrylate, with the polybutadiene in amaster batch prior to blending with other core components.

[0046] Free radical initiators are used to promote cross-linking of thebase rubber and the cross-linking agent. Suitable free radicalinitiators for use in the golf ball core 12 of the present inventioninclude peroxides such as dicumyl peroxide, bis-(t-butyl peroxy)diisopropyl benzene, t-butyl perbenzoate, di-t-butyl peroxide,2,5-dimethyl-2,5-di-5-butylperoxy-hexane, 1,1-di (t-butylperoxy)3,3,5-trimethyl cyclohexane, and the like, all of which are readilycommercially available.

[0047] Zinc oxide is also preferably included in the core formulation.Zinc oxide may primarily be used as a weight adjusting filler, and isalso believed to participate in the cross-linking of the othercomponents of the core (e.g. as a coagent). Additional processing aidssuch as dispersants and activators may optionally be included. Inparticular, zinc stearate may be added as a processing aid (e.g. as anactivator). Any of a number of specific gravity adjusting fillers may beincluded to obtain a preferred total weight of the core 12. Examples ofsuch fillers include tungsten and barium sulfate. All such processingaids and fillers are readily commercially available. One tungsten filleris WP102 Tungsten (having a 3 micron particle size) available fromAtlantic Equipment Engineers of New Jersey.

[0048] Table One below provides the ranges of materials included in thepreferred core formulations of the present invention. TABLE ONEComponent Preferred Range Most Preferred Rang Polybutadiene 100 parts100 parts Zinc diacrylate 20-35 phr 25-30 phr Zinc oxide 0-50 phr  5-15phr Zinc stearate 0-15 phr  1-10 phr Peroxide 0.2-2.5 phr 0.5-1.5 phrFiller As desired As desired (e.g. tungsten) (e.g. 2-10 phr) (e.g. 2-10phr)

[0049] In the present invention, the core components are mixed andcompression molded in a conventional manner known to those skilled inthe art. In a preferred form, the finished core 12 has a diameter ofabout 1.35 to about 1.64 inches for a golf ball 10 having an outerdiameter of 1.68 inches. The core weight is preferably maintained in therange of about 32 to about 40 g. The core PGA compression is preferablymaintained in the range of about 50 to 90, and most preferably about 55to 80.

[0050] As used herein, the term PGA compression is defined as follows:

[0051] PGA compression value=180 Riehle compression value

[0052] The Riehle compression value is the amount of deformation of agolf ball in inches under a static load of 200 pounds, multiplied by1000. Accordingly, for a deformation of 0.095 inches under a load of 200pounds, the Riehle compression value is 95 and the PGA compression valueis 85.

[0053] If the golf ball 10 has a boundary layer 14, the boundary layer14 is preferably composed of a thermoplastic material. Suitablethermoplastic materials for the boundary layer 14 include: HYTREL®and/or HYLENE® products from DuPont, Wilmington, Del.; PEBAX® productsfrom Elf Atochem, Philadelphia, Pa.; SURLYN® products from DuPont;and/or ESCOR® or IOTEK® products from Exxon Chemical, Houston, Tex.

[0054] The Shore D hardness of the boundary layer 14 preferably rangesfrom 50 to 75, as measured according to ASTM D-2290. In a most preferredembodiment, the boundary layer 14 has a Shore D hardness in the range of58-65. One reason for preferring a boundary layer 14 with a Shore Dhardness of 75 or lower is to improve the feel of the resultant golfball it is also preferred that the boundary layer 14 is composed of ablend of SURLYN® ionomer resins. SURLYN® 8150, 9150, and 6320 are,respectively, an ionomer resin composed of a sodium neutralizedcopolymer of ethylene and methacrylic acid, an ionomer resin composed ofa zinc neutralized copolymer of ethylene and methacrylic acid, and anionomer resin composed of a terpolymer of ethylene, methacrylic acid andn-butyl acrylate partially neutralized with magnesium. The optionalboundary layer 14 is preferably composed of a blend of these ionomers.

[0055] One formulation for the optional boundary layer 14 has 25-50weight percent SURLYN 8150, 25-50 weight percent SURLYN 9150, and 25-50weight percent SURLYN 6320. Another formulation for the optionalboundary layer 14 has 25-75 weight percent SURLYN 9150, and 25-75 weightpercent SURLYN 6320. Those skilled in the pertinent art will recognizethat other ionomers may be utilized for the optional boundary layer 14without departing from the scope and spirit of the present invention.The Shore D hardness of the boundary layer 14 is preferably 50 to 75,more preferably from 55-65 Shore D, and most preferably 58-63 Shore D,as measured according to ASTM-D2240.

[0056] The polyurethane material of the present invention preferably hasa Shore D hardness ranging from 30 to 60 as measured according toASTM-D2240, more preferably 40 to 55 Shore D, and most preferably 50Shore D.

[0057] A preferred formulation for the polyurethane material of thepresent invention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to 75 partsper one hundred parts of the curative blend andN,N′-dialkylamino-diphenyl-methane in an amount of 25 to 75 parts perone hundred parts of the curative blend, and 1 to 10 parts of a triolsuch as trimetholylpropane (TMP).

[0058] A most preferred formulation for the polyurethane material of thepresent invention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 50 parts per onehundred parts of the curative blend andN,N′-dialkylamino-diphenyl-methane in an amount of 50 parts per onehundred parts of the curative blend, and 3 parts TMP.

[0059] An alternative formulation for the polyurethane material of thepresent invention is polyether terminated toluene diisocyanateprepolymer (NCO content of 6%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 55 parts per onehundred parts of the curative blend andN,N′-dialkylamino-diphenyl-methane in an amount of 45 parts per onehundred parts of the curative blend, and 3 parts TMP, which provided apolyurethane material with a Shore D hardness of approximately 50points.

[0060] Yet another alternative formulation for the polyurethane materialof the present invention is polytetramethylene ether glycol terminatedtoluene diisocyanate prepolymer (NCO content of 5%), a curative blendcomprising 4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 65parts per one hundred parts of the curative blend andN,N′-dialkylamino-diphenyl-methane in an amount of 35 parts per onehundred parts of the curative blend, and 3 parts TMP, which provided apolyurethane material with a Shore D hardness of approximately 50points.

[0061] Yet another alternative formulation for the polyurethane materialof the present invention is polytetramethylene ether glycol terminatedtoluene diisocyanate prepolymer (NCO content of 5%), a curative blendcomprising 4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to75 parts per one hundred parts of the curative blend anddimethylthio-2,4-toluene-diamine in an amount of 25 to 75 parts per onehundred parts of the curative blend.

[0062] The preferred construction of a golf ball 10 utilizing thepolyurethane material of the present invention is a three-piece solidgolf ball having a solid polybutadiene core 12, a boundary layer 14composed of a blend of ionomers, and a cover 16 composed of thepolyurethane material of the present invention. The core 12 ispreferably compression molded, the boundary layer 14 is preferablyinjection molded, and the cover 16 is preferably cast. The golf ball 10may be finished with one or two layers of a base white coating, a clearcoating and an indicia.

[0063] The thickness of the cover 16 preferably ranges from 0.010 inchto 0.070 inch, more preferably ranges from 0.014 inch to 0.050 inch,even preferably ranges from 0.015 inch to 0.044 inch, most preferablyranges from 0.025 inch to 0.040 inch, and is most preferably 0.030 inch.The boundary layer 14 is preferably injection molded and preferablyranges in thickness from 0.040 inch to 0.090 inch, more preferably from0.045 inch to 0.070 inch, and most preferably from 0.050 inch to 0.060inch. The boundary layer 14 may also be compression molded from halfshells. The core 12 preferably has a diameter of between 1.35 inches and1.60 inches, more preferably between 1.45 inches and 1.55 inches, andmost preferably 1.49 inches. The core 12 preferably has a PGAcompression ranging from 70-110 points, and most preferably 100 points.A more detailed description of a construction and performance propertiesof a golf ball utilizing the polyurethane material of the presentinvention is set forth in co-pending U.S. patent application Ser. No.09/877,651 for a Golf Ball With A High Coefficient Of Restitution, filedon Jun. 8, 2001, assigned to Callaway Golf Company, and co-pending U.S.patent application Ser. No. 09/682,792 for a Golf Ball With A HighCoefficient Of Restitution, filed on Oct. 19, 2001, assigned to CallawayGolf Company, both of which are hereby incorporated by reference intheir entireties.

[0064] The Shore D hardness of the golf ball 10, as measured on the golfball, is preferably between 40 Shore D points to 75 Shore D points, andmost preferably between 50 Shore D points and 65 Shore D points. Thehardness of the golf ball 10 is measured using an Instron Shore DHardness measurement device wherein the golf ball 10 is placed within aholder and the pin is lowered to the surface to measure the hardness.The average of five measurements is used in calculating the ballhardness. The ball hardness is preferably measured on a land area of thecover 14. The preferred overall diameter of the golf ball 10 isapproximately 1.68 inches, and the preferred mass is approximately 45.5grams. However, those skilled in the pertinent art will recognize thatthe diameter of the golf ball 10 may be smaller (e.g. 1.65 inches) orlarger ( e.g. 1.70 inches) without departing from the scope and spiritof the present invention. Further, the mass may also vary withoutdeparting from the scope and spirit of the present invention.

[0065] The surface geometry of the golf ball 10 is preferably aconventional dimple pattern such as disclosed in U.S. Pat. No. 6,213,898for a Golf Ball With An Aerodynamic Surface On A Polyurethane Cover,which pertinent parts are hereby incorporated by reference.Alternatively, the surface geometry of the golf ball 10 may have anon-dimple pattern such as disclosed in U.S. Pat. No. 6,290,615 filed onNov. 18, 1999 for A Golf Ball Having Tubular lattice Pattern, whichpertinent parts are hereby incorporated by reference.

[0066] The polyurethane material of the present invention provides agolf ball cover 16 with greater durability than most other polyurethanecovers. Cover durability is determined according to the followingprocedure. A CALLAWAY GOLF® STEELHEAD™ X-14 ® PRO SERIES sand wedge wasused on a GOLF LABS robot to strike twelve golf balls per sample twice(the balls were hit on each side) and to strike six control golf ballstwice. The golf ball is placed on a tee with the pole positioned forimpact with the club. The impact area is sprayed with water. The robotis triggered, the club is swung at approximately 72 miles per hour, andthe wet golf ball is struck. The golf ball retrieved and placed on thetee with the opposite side of the pole positioned for impact and sprayedwith water. The robot is triggered and the wet golf ball is againstruck. The club face and grooves of the sand wedge are cleaned anddried prior to each hit. The golf ball is retrieved and examined under astereoscopic microscope for evaluation and ranking. The results areanalyzed using statistics with a 95% confidence level.

[0067] The cover durability is ranked according to the followingcriteria:1Portion of cover has been completely sheared off. Dimples (orother surface geometry) have been reduced or greatly removed;2Covermaterial has been sheared to the extent that flaps of cover are visible,but not severe enough to completely shear off and remove dimples;3Moderate cutting of the cover material is evident to the extent thatinternal portions of the cover are exposed, but the cover is stillintact;3.5Slight cutting of the cover material is evident with little orno internal portions of the cover exposed, bunching of the cover isapparent from a side or profile view;3.75Slight cutting of the covermaterial is evident with little or no internal portions of the coverexposed, and no bunching of the cover is apparent from a side or profileview;4Indentations in the cover are evident, but there is no bunching ofthe cover material;4.5Groove marks are clearly defined, but nodeformation of the cover material is apparent; 5Groove marks aredifficult to see and slight score marks may be visible, but the finishis not cracked or broken and there is no damage to the cover material.

[0068] Golf balls utilizing the polyurethane material of the presentinvention were compared to the CALLAWAY GOLF® CTU30™ BLUE golf ball, theCALLAWAY GOLF® CTU30™ RED golf ball, the TITLEIST® PROV1™ golf ball andthe MAXFLI® A10 golf ball, all of which have thermosetting polyurethanecovers. The CTU30™ RED golf ball had a 2.42 ranking, the CTU30™ BLUEgolf ball had a 2.69 ranking, the PROV1™ golf ball had a 2.63 rankingand the A10™ golf ball had a 2.58 ranking. The golf balls that utilizedthe polyurethane cover of the present invention had a ranking rangingfrom 2.89 to 3.34.

[0069] From the foregoing it is believed that those skilled in thepertinent art will recognize the meritorious advancement of thisinvention and will readily understand that while the present inventionhas been described in association with a preferred embodiment thereof,and other embodiments illustrated in the accompanying drawings, numerouschanges, modifications and substitutions of equivalents may be madetherein without departing from the spirit and scope of this inventionwhich is intended to be unlimited by the foregoing except as may appearin the following appended claims. Therefore, the embodiments of theinvention in which an exclusive property or privilege is claimed aredefined in the following appended claims.

I claim as my invention:
 1. A golf ball comprising: a core; and a coverformed over the core, the cover composed of a thermosetting polyurethanematerial formed from reactants comprising at least one polyurethaneprepolymer and a curative blend comprising4,4″-methylenebis-(2,6-diethyl)-aniline and a second curing agent;wherein the cover has an aerodynamic surface geometry thereon.
 2. Thegolf ball according to claim 1 further comprising at least one boundarylayer disposed between the core and the cover.
 3. The golf ballaccording to claim 1 wherein the polyurethane prepolymer is apolypropylene glycol terminated toluene diisocyanate prepolymer with anitrogen-carbon-oxygen content ranging from 3.0% to 6.0%.
 4. The golfball according to claim 2 wherein the boundary layer is composed of ablend of ionomers.
 5. The golf ball according to claim 1 wherein thepolyurethane prepolymer is a polytetramethylene ether glycol terminatedtoluene diisocyanate prepolymer with a nitrogen-carbon-oxygen contentranging from 3.75% to 7.0%.
 6. A golf ball comprising: a core comprisinga polybutadiene mixture; a boundary layer formed over the core; and acover formed over the boundary layer, the cover composed of athermosetting polyurethane material formed from reactants comprising atleast one polyurethane prepolymer and a curative blend comprising4,4″-methylenebis-(2,6-diethyl)-aniline in an amount of 65 parts per onehundred parts of the curative blend andN,N″-dialkylamino-diphenyl-methane in an amount of 35 parts per onehundred parts of the curative blend; wherein the cover has anaerodynamic surface geometry thereon.
 7. A golf ball comprising: a corecomprising a polybutadiene mixture, the core having a diameter rangingfrom 1.35 inches to 1.64 inches and having a PGA compression rangingfrom 50 to 90; a boundary layer formed over the core, the boundary layercomposed of a blend of ionomer materials, the boundary layer having athickness ranging from 0.020 inch to 0.075 inch, the blend of ionomermaterials having a Shore D hardness ranging from 50 to 75 as measuredaccording to ASTM-D2240; and a cover formed over the boundary layer, thecover composed of a thermosetting polyurethane material formed fromreactants comprising polytetramethylene ether glycol terminated toluenediisocyanate prepolymer and a curative comprising4,4″-methylenebis-(2,6-diethyl)-aniline, wherein the thermosettingpolyurethane material has a Shore D hardness ranging from 30 to 60 asmeasured according to ASTM-D2240, a thickness ranging from 0.015 inch to0.044 inch, and an aerodynamic surface geometry thereon.
 8. A golf ballcomprising: a core; and a cover formed over the core, the cover composedof a thermosetting polyurethane material formed from reactantscomprising at least one polyurethane prepolymer and a curative blendcomprising 4,4″-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to75 parts per one hundred parts of the curative blend and a second curingagent in an amount of 25 to 75 parts per one hundred parts of thecurative blend, wherein the second curing agent has the same equivalentweight as the 4,4″-methylenebis-(2,6-diethyl)-aniline; wherein the coverhas an aerodynamic surface geometry thereon.